Process for manufacturing titanium compounds using a reducing agent

Abstract

A process is provided for the manufacture of titanium compounds and particularly titanium dioxide wherein excess titaniferous bearing material is reacted with dilute sulfuric acid having a concentration of between about 25% and about 60% by weight at a temperature below about 140° C., and in the presence of a reducing agent which affects the reduction of ferric iron to ferrous iron. Thereafter, the titanium sulfate may be recovered or further processed to provide titanium dioxide hydrate accompanied by recycling the spent acid for reaction with the titaniferous bearing material charged to the process. The titanium hydrate may be calcined to provide titanium dioxide.

We claim: 
     
       1. A process for producing a titanium sulphate solution which comprises reacting (a) a titaniferous bearing material in an amount between about 10% and about 400% above the stoichiometric amount of titaniferous bearing material necessary to react with sulfuric acid to provide titanium sulphate, and   (b) a dilute sulfuric acid solution having a concentration between about 25% and about 60% by weight, based upon the total weight of said solution, at a temperature below about 140° C., in the presence of a reducing agent which effects the reduction of ferric iron to ferrous iron; cooling the resulting reaction mixture to a temperature below 110° C. without precipitating the reaction products to produce a reaction mixture containing titanium sulfate; and separating undissolved solids to produce a titanium sulfate solution.     
     
     
       2. The process of claim 1 wherein the reaction between said titaniferous bearing material and said dilute sulfuric acid solution is conducted at a temperature between about 55° C. and about 140° C. 
     
     
       3. The process of claim 1 wherein said resulting reaction mixture is cooled to a temperature of about 75° C. 
     
     
       4. The process of claim 1 wherein the reducing agent is selected from the group consisting of metallic tin, iron, zinc, zirconium, titanium, aluminum, magnesium and alloys thereof, sulfurous acid, sodium thiosulfate, sulfur dioxide, titanous sulfate, reduced ilmenite and mixtures thereof. 
     
     
       5. The process of claim 1 wherein the reducing agent is present in the reaction in at least stoichiometric amounts to the quantity of ferric iron present. 
     
     
       6. A process for producing titanium dioxide which comprises (1) reacting (a) a titaniferous bearing material in an amount between about 10% and about 400% above the stoichiometric amount of titaniferous bearing material necessary to react with sulfuric acid to provide titanium sulphate, and   (b) a dilute sulfuric acid solution having a concentration between about 25% and about 60% by weight, based upon the total weight of said solution, at a temperature below about 140° C., in the presence of a reducing agent which effects the reduction of ferric iron to ferrous iron; (2) cooling the resulting reaction mixture to a temperature below about 110° C. without precipitating the reaction products; (3) removing undissolved solids and iron sulfate from said reaction mixture to provide a titanium sulphate solution; (4) hydrolyzing said titanium sulphate solution to provide a hydrate of titanium dioxide and spent sulfuric acid solution; (5) calcining said hydrate of titanium dioxide to provide titanium dioxide and (6) recovering the titanium dioxide.     
     
     
       7. The process of claim 6 wherein the reaction between said titaniferous bearing material and said dilute sulfuric acid is conducted at a temperature between about 55° C. and about 140° C. 
     
     
       8. The process of claim 6 wherein the reaction mixture is cooled to a temperature below about 75° C. 
     
     
       9. The process of claim 6 which includes passing the undissolved solids and reductant to reaction step (1) for reaction with sulfuric acid. 
     
     
       10. The process of claim 6 which includes passing the spent sulfuric acid solution from hydrolysis step (4) to reaction step (1) for reaction with titaniferous bearing material. 
     
     
       11. The process of claim 6 wherein the reducing agent is selected from the group consisting of metallic tin, iron, zinc, zirconium, titanium, aluminum, magnesium and alloys thereof, sulfurous acid, sodium thiosulfate, sulfur dioxide, titanous sulfate, reduced ilmenite and mixtures thereof. 
     
     
       12. The process of claim 6 wherein the reducing agent is present in the reaction in at least stoichiometric amounts to the quantity of ferric iron present. 
     
     
       13. A continuous process for producing titanium dioxide which comprises: (1) continuously reacting (a) a titaniferous bearing material in an amount between about 10% and about 400% above the stoichiometric amount of titaniferous bearing material necessary to react with sulfuric acid to provide titanium sulphate, and (b) a dilute sulfuric acid solution having a concentration between about 25% and about 60% by weight, based upon the total weight of said solution, at a temperature below about 140° C., in the presence of a reducing agent which effects the reduction of ferric iron to ferrous iron in at least stoichiometric amounts to the quantity of ferric iron present,   (2) cooling the resulting reaction mixture to a temperature below about 110° C. in a second reaction vessel without precipitating the reaction mixture while continuing the reaction;   (3) separating unreacted titaniferous bearing material from the reaction mixture to provide a solution of iron sulphate and titanium sulphate;   (4) removing iron sulphate from said solution of iron sulphate and titanyl sulphate to provide a solution of titanium sulphate;   (5) hydrolyzing said titanium sulphate solution to provide a titanium dioxide hydrate, and spent sulfuric acid solution;   (6) calcining said titanium dioxide hydrate to provide titanium dioxide and;   (7) recovering titanium dioxide.   
     
     
       14. The process of claim 13 wherein the reducing agent is selected from the group consisting of metallic tin, iron, zinc, zirconium, titanium, aluminum, magnesium and alloys thereof, sulfurous acid, sodium thiosulfate, sulfur dioxide, titanous sulfate, reduced ilmenite and mixtures thereof.